Modified composite fiber film and its LBL self-assembly methods and applications
Technical field
The present invention relates to Material Field more particularly to a kind of modified composite fiber film and its LBL self-assembly method and answer
With.
Background technique
LBL self-assembly is that a kind of simple and effective, versatile and flexible, repeatable have for decorative material surface, preparation height
The technology of the plural layers of sequence.In addition, LBL self-assembly is able to achieve the regulation of nano grade membrane thickness degree and bottom plate and film forming matter select
It is applied to the fields such as catalysis, detection and biomaterial extensively, gradually develops into a kind of more mature multilayer film preparation skill
Art.Layer-by-layer can be divided into infusion method, spin-coating method, spray-on process etc. according to the mode difference of self assembly, wherein by visiting
Study carefully, apply it is most commonly used be infusion method.Impregnate LBL self-assembly mainly pass through electrostatic force, hydrogen bond etc. drive hydrophilic bottom plate with
Multilayer functional fiber film is constructed between film forming matter and film forming matter.
However, having many advantages, such as the tunica fibrosa of good mechanical property, large specific surface area for many, due to no enough tables
Surface charge and water-wetted surface and cannot function as impregnate LBL self-assembly bottom plate so that LBL self-assembly bottom plate selection and answer
With receiving certain limitation.For this purpose, how to increase the surface charge and wetting of tunica fibrosa by simple and effective method of modifying
Property be to solve the limited key point of LBL self-assembly bottom plate selection.However common surface modifying method has vulcanization, aura to put
Electricity, ultraviolet irradiation etc., limitation are low efficiency, time are long, environmental pollution is serious etc..
Summary of the invention
The present invention for the technical problems in the prior art, provide a kind of surface charge that can increase tunica fibrosa and
Wetability, the easy to operate and modified composite fiber film and its LBL self-assembly methods and applications that keep bottom plate range of choice wide.
The technical scheme to solve the above technical problems is that
A kind of modified composite fiber film layer layer self-assembling method, includes the following steps:
Prepare it is hydrophobic it is micro-/receive macromolecular fibre film;
To it is described it is hydrophobic it is micro-/receive macromolecular fibre film surface carry out plasma modification, obtain bottom plate;
The polyelectrolyte A of oppositely charged and polyelectrolyte B are alternately assembled into institute using layer-by-layer is impregnated
State on bottom plate, until reach the required double-deck number to get.
In one of the embodiments, it is described it is hydrophobic it is micro-/receive macromolecular fibre ilm substrate material be selected from collagen, silk
Fibroin, chitosan and its derivative, polymethyl methacrylate, polystyrene, polyacrylonitrile, gathers in oneself cellulose acetate
One of ester copolymer is a variety of.
In one of the embodiments, it is described it is hydrophobic it is micro-/receive macromolecular fibre film by method of electrostatic spinning, dry spinning method,
Wet spinning process, phase separation method, centrifugal spinning, composite spinning method, molecular spinneret, any in composite spinning method
Kind is prepared.
Hydrophobic micro-/macromolecular fibre the film of receiving is prepared by method of electrostatic spinning in one of the embodiments, technique
Parameter are as follows: electrostatic spinning voltage is 16-22kV, and solution flow velocity is 0.7mL/h-1.2mL/h, and receiving distance is 15cm, and temperature is
15 DEG C -30 DEG C, relative humidity 35%-40%.
The conditional parameter of the plasma modification in one of the embodiments, are as follows: working gas is selected from oxygen, nitrogen
One of gas, helium and argon gas are a variety of, and plasma treatment power is 70W-180W, and the processing time is 30s~110s, back end
Vacuum degree is 30Pa, gas flow rate 55cm3/min-65cm3/min。
The absolute value of the zeta current potential of the bottom plate is not less than 10mV in one of the embodiments,.
The polyelectrolyte A or the polyelectrolyte B are selected from and can be dispersed or dissolved in one of the embodiments,
Synthesis high molecular material, natural macromolecular material and micro-/ nano particle in water or organic solvent.
The polyelectrolyte A is selected from least one of chitosan and lysozyme in one of the embodiments,;It is described poly-
Electrolyte B is selected from one of bovine serum albumin(BSA), fibroin albumen and collagen or a variety of.
Described use impregnates layer-by-layer for the polyelectrolyte A of oppositely charged in one of the embodiments,
It further include unassembled to the bottom plate using cleaning solution cleaning in the step being alternately assembled on the bottom plate with polyelectrolyte B
On polyelectrolyte A and the step of polyelectrolyte B.
The modified composite fiber prepared by modified composite fiber film layer layer self-assembling method described in any of the above embodiments
Film.
The application of modified composite fiber film described above in cell culture.
The beneficial effects of the present invention are:
Compared with tradition layer by layer self-assembling method, modified composite fiber film layer layer self-assembling method of the invention passes through preparatory
To it is hydrophobic it is micro-/receive macromolecular fibre film surface carry out plasma modification (material surface band is made not by different modified gas
With charge), it is hydrophobic it is micro-/receive the surface of macromolecular fibre film (be different from Conventional solid matrix) and introduce the same of a large amount of free radicals
When be unaffected its pattern, while enhance its wettability of the surface, so as to realize after modification it is micro-/receive height
LBL self-assembly forms to have with the polyelectrolyte of opposite charges on molecular fiber film (bottom plate) promotes cell proliferation ability etc.
The modified composite fiber film of performance can make material tool that is originally hydrophobic and should not be used in the fields such as biological medicine, environmental protection
Standby good biocompatibility is significantly expanded the range of choice of macromolecular fibre ilm substrate, while expanding and working as its application range.This hair
Bright modified composite fiber film layer layer self-assembling method is easy to operate, at home and abroad all still belongs to the first time and uses plasma modification technology
In reinforcing fiber film surface charge and hydrophily to assist it to carry out layer assembly.
Plasma modification is a kind of easy to operate, high-efficient, environmentally friendly method of modifying.According to plasma modification institute
Gas is different, can make it is hydrophobic it is micro-/receive macromolecular fibre film the Kinds of Free Radicals that is loaded of surface it is different and with different electricity
The charge of property, while its wettability of the surface can be enhanced, consequently facilitating carrying out the layer assembly of subsequent polyelectrolyte.For example, making
When modified with oxygen plasma, it is hydrophobic it is micro-/receive a large amount of oxygen radicals of area load of macromolecular fibre ilm substrate, as hydroxyl,
Carboxyl increases its surface negative charge;Conversely, when being modified using nitrogen, it is hydrophobic it is micro-/receive the table of macromolecular fibre ilm substrate
Face load contains nitrogen free radical, such as amino, increases its film surface positive charge.Therefore, bottom is prepared using preparatory plasma modification
Plate can expand the range of choice of self-assembling method insole board layer by layer, thus the application range of further expansion LBL self-assembly, example
Such as make originally hydrophobic and should not be used in biological medicine, the material in environmental protection field can be used for cell culture.
Detailed description of the invention
A is the scanning electron microscope (SEM) photograph of polystyrene micro/nano-fibre film in Fig. 1, and b is modified polystyrene micro-/ nano
The scanning electron microscope (SEM) photograph of tunica fibrosa.
A is the modified composite micro/nano tunica fibrosa of polystyrene-chitosan-bovine serum albumin that the double-deck number is 5 in Fig. 2
Scanning electron microscope (SEM) photograph is shown in that Fig. 2 b is the modified composite micro/nano fiber of polystyrene-chitosan-bovine serum albumin that the double-deck number is 5.5
The scanning electron microscope (SEM) photograph of film.
Fig. 3 is polystyrene micro/nano-fibre film and modified polystyrene micro/nano-fibre film prepared by embodiment 1
Contact angle and its optical photograph, wherein a refers to that polystyrene micro/nano-fibre film, b refer to poly- after the modified 70s of oxygen plasma
Styrene micro/nano-fibre film, c refer to that chitosan/bovine serum albumin/Polystyrene composite micro/nano that the double-deck number is 5 is fine
Film is tieed up, d refers to that the double-deck number is 5.5 chitosan/bovine serum albumin/Polystyrene composite micro/nano tunica fibrosa.
Fig. 4 be embodiment 1 prepare polystyrene micro/nano-fibre film, modified polystyrene micro/nano-fibre film and
The zeta potential diagram of LBL self-assembly solution.Wherein, a refers to that polystyrene micro/nano-fibre film, b refer to bovine serum albumen solution, c
Refer to that the polystyrene micro/nano-fibre film after the modified 70s of oxygen plasma, d refer to that the double-deck number is 5 chitosan/cow's serum egg
White/Polystyrene composite micro/nano tunica fibrosa, e refer to that the double-deck number is that 5.5 chitosan/bovine serum albumin/polystyrene changes
Property composite micro/nano tunica fibrosa, f refer to chitosan solution.
Fig. 5 is the modified micro/nano-fibre film of composite polystyrene/chitosan/bovine serum albumin prepared using embodiment 1
Electron microscope and fluorogram after cultivating cell.Wherein, Fig. 5-a is composite polystyrene/chitosan/bovine serum albumin micro-/ nano
Through dyeing the cell proliferation data obtained after fiber Membrance cuiture cell.
Specific embodiment
The principle and features of the present invention will be described below with reference to the accompanying drawings, and the given examples are served only to explain the present invention, and
It is non-to be used to limit the scope of the invention.Unless otherwise defined, all technical and scientific terms used herein and belong to this
The normally understood meaning of those skilled in the art of invention is identical.Art as used herein in the specification of the present invention
Language, which is only for the purpose of describing specific embodiments, is not intended to limit the present invention.
Embodiment 1
The present embodiment provides a kind of modified composite fiber film layer layer self-assembling methods, include the following steps:
S1 prepares polystyrene micro/nano-fibre film (PS) by electrostatic spinning technique.
Specifically, the mixing for polystyrene being dissolved in tetrahydrofuran and n,N-Dimethylformamide (mass ratio 1:1) is molten
In liquid, the polystyrene solution of 10wt% is obtained.Then polystyrene micro/nano-fibre film is prepared by electrostatic spinning technique
(PS), technological parameter are as follows: electrostatic spinning voltage is 20kV, and solution flow velocity is 1mL/h, and receiving distance is 15cm, and temperature is 25 DEG C,
Relative humidity is 40%.Then resulting polystyrene micro/nano-fibre film is placed at 60 DEG C and is dried in vacuo, residual solvent is made
Sufficiently volatilization.
S2 carries out plasma modification to polystyrene micro/nano-fibre film, obtains the bottom plate of a large amount of negative electrical charges of surface band
(PSO)。
Specifically, the polystyrene micro/nano-fibre film that step S1 is prepared is placed in low-temperature plasma instrument reaction chamber
On interior glass plate, oxygen air valve is opened, its air pressure is made to maintain 0.2MPa or so.Oxygen plasma response parameter is set: back
Bottom vacuum degree is 30Pa, gas flow rate 60cm3/ min, power 100W, processing time are 70s.
Measure the zeta current potential and wetability of the modified polystyrene micro/nano-fibre film of oxygen plasma.
S3, using impregnating layer-by-layer for the chitosan (CS) and bovine serum albumin(BSA) (BSA) of oppositely charged
Alternating is assembled into bottom plate (PSO) on, until reaching the required double-deck number.
Specifically, Chitosan powder is added in the acetic acid solution of 0.5% (v/v), it is molten is configured to 1mg/mL chitosan
Liquid, and adjust pH to 5.Bovine serum albumin powder is add to deionized water, is configured to 1mg/mL bovine serum albumen solution, and adjust
PH to 5.5.
The modified bottom plate (the hydrophile polystyrene micro/nano-fibre film with a large amount of negative electricity) of step S2 is dipped into positively charged
Chitosan solution in, come into full contact with bottom plate with solution, after twenty minutes take out bottom plate, it is clear using the sodium chloride solution of 0.1M
It washes three times, removes the unassembled successful chitosan of film surface, form the bottom plate with first layer chitosan.It will gather again with first layer shell
The bottom plate of sugar is dipped into electronegative bovine serum albumen solution, is come into full contact with film with solution, is taken the film out after twenty minutes, adopts
It is cleaned three times with the sodium chloride solution of 0.1M, removes the unassembled successful bovine serum albumin(BSA) of film surface, form band first layer ox
Sero-abluminous bottom plate so far successfully assembles a bilayer.Be repeated in bottom plate of the above-mentioned formation with first layer chitosan and
The step of forming the bottom plate with first layer bovine serum albumin(BSA), until the double-deck number reaches 5 or 5.5, drying is to get polystyrene-
The modified composite micro/nano tunica fibrosa PS of chitosan-bovine serum albuminO-(CS/BSA)。
In addition, in the present embodiment, gained polystyrene micro/nano-fibre film and its pattern after plasma modification are shown in
Fig. 1, wherein Fig. 1-a is polystyrene micro/nano-fibre film scanning electron microscope (SEM) photograph, and Fig. 1-b is after the modified 70s of oxygen plasma
Polystyrene micro/nano-fibre film scanning electron microscope (SEM) photograph.In identical scanning multiple it can be seen from the comparison of Fig. 1 a and Fig. 1 b
Under, the more modified polystyrene micro/nano-fibre of polystyrene micro/nano-fibre is slightly thick.
The fiber morphology figure that LBL self-assembly obtains after polystyrene micro/nano-fibre membrane modifying is shown in Fig. 2, wherein Fig. 2-a
It is chitosan/bovine serum albumin/polystyrene micro/nano-fibre film that the double-deck number is 5 and 5.5 respectively with Fig. 2-b.It can by Fig. 2
To find out, the modified composite micro/nano fiber film surface of polystyrene-chitosan through LBL self-assembly preparation-bovine serum albumin
It is more smooth compared with polystyrene micro/nano-fibre film surface.
The contact angle and its optical photograph of styrene micro/nano-fibre film and modified polystyrene micro/nano-fibre film are shown in
Fig. 3.As seen from Figure 3, the polystyrene micro/nano-fibre film after the 70s of plasma modification and chitosan/cow's serum egg
In a very short period of time, water contact angle becomes 0 to white/Polystyrene composite micro/nano tunica fibrosa, illustrates modified nanometer
Tunica fibrosa has fabulous hydrophily.
Polystyrene micro/nano-fibre it can be seen from the zeta potential diagram of Fig. 4 after the modified 70s of oxygen plasma
The negative charge amount of film surface band is more compared with polystyrene micro/nano-fibre film.Chitosan/bovine serum albumin/polyphenyl second that bilayer is 5
Alkene is modified composite micro/nano tunica fibrosa PSO-(CS/BSA)5Surface is negatively charged, and the double-deck chitosan/bovine serum albumin for being 5.5/
Polystyrene composite micro/nano tunica fibrosa PSO-(CS/BSA)5.5Surface is positively charged.This is because double-deck answer for 5 modification
To close micro/nano-fibre film outermost layer be bovine serum albumin, and double-deck for 5.5 is then chitosan.
Composite polystyrene/chitosan/bovine serum albumin micro/nano-fibre film that embodiment 1 obtains is used to mouse to close
Save cultured chondrocytes.Cultivated composite polystyrene/chitosan/bovine serum albumin micro/nano-fibre film shape appearance figure of cell
Fig. 5 is seen with fluorogram.Cell proliferation data are shown in Fig. 5-a, the results showed that answer by prepared by plasma modification and LBL self-assembly
It closes polystyrene/chitosan/bovine serum albumin micro/nano-fibre film to grow favorably cell, conversely, being modified or only passing through
The film of LBL self-assembly can't promote cell proliferation.
Embodiment 2
The present embodiment provides a kind of modified composite fiber film layer layer self-assembling methods, include the following steps:
S1 prepares polymethyl methacrylate micro/nano-fibre film by electrostatic spinning technique.
Specifically, polyacrylonitrile is dissolved in tetrahydrofuran solution, obtains the polyacrylonitrile solution of 10wt%.Then lead to
It crosses electrostatic spinning technique and prepares polymethyl methacrylate micro/nano-fibre film, technological parameter are as follows: electrostatic spinning voltage is
20kV, solution flow velocity are 1mL/h, and receiving distance is 15cm, and temperature is 25 DEG C, relative humidity 40%.It then will be resulting poly-
Methyl methacrylate micro/nano-fibre film, which is placed at 60 DEG C, to be dried in vacuo, and residual solvent is made sufficiently to volatilize.
S2 carries out plasma modification to polymethyl methacrylate micro/nano-fibre film, obtains a large amount of negative electrical charges of surface band
Bottom plate.
Specifically, the polymethyl methacrylate micro/nano-fibre film that step S1 is prepared is placed in low-temperature plasma
On glass plate in instrument reaction chamber, argon gas air valve is opened, its air pressure is made to maintain 0.2MPa or so.Argon plasma is arranged to react
Parameter: back end vacuum degree is 30Pa, gas flow rate 60cm3/ min, power 150W, processing time are 90s.
Measure zeta current potential and the wetting of the modified polymethyl methacrylate micro/nano-fibre film of argon plasma
Property.
The chitosan of oppositely charged and fibroin albumen are alternately assembled into bottom plate using layer-by-layer is impregnated by S3
On, until reaching the required double-deck number.
Specifically, Chitosan powder is added in the acetic acid aqueous solution of 0.5% (V/V), is configured to 1mg/mL chitosan
Solution, and adjust pH to 5.Fibroin albumen is add to deionized water, 1mg/mL silk fibroin protein solution is configured to, and adjusts pH extremely
5.3。
Step S2 modified bottom plate (the hydrophilic polymethyl methacrylate micro/nano-fibre film with a large amount of negative electricity) is impregnated
It into positively charged chitosan solution, comes into full contact with bottom plate with solution, after twenty minutes takes out bottom plate, using the chlorination of 0.1M
Sodium solution cleans three times, removes the unassembled successful chitosan of film surface, forms the bottom plate with first layer chitosan.Again by band
The bottom plate of one layer of chitosan is dipped into electronegative silk fibroin protein solution, comes into full contact with film with solution, after twenty minutes by film
It takes out, is cleaned three times using the sodium chloride solution of 0.1M, remove the unassembled successful fibroin albumen of film surface, form band first layer
The bottom plate of fibroin albumen so far successfully assembles a bilayer.It is repeated in bottom plate and shape of the above-mentioned formation with first layer chitosan
The step of at bottom plate with first layer fibroin albumen, until the double-deck number reaches 5 or 5.5, it is dry to get poly-methyl methacrylate
The protein modified composite micro/nano tunica fibrosa of ester-Properties of Chitosan Fibroin Blend.
Embodiment 3
The present embodiment provides a kind of modified composite fiber film layer layer self-assembling methods, include the following steps:
S1 prepares polyacrylonitrile micro/nano-fibre film by electrostatic spinning technique.
Specifically, polyacrylonitrile is dissolved in n,N-Dimethylformamide solution, the polyacrylonitrile for obtaining 10wt% is molten
Liquid.Then polyacrylonitrile micro/nano-fibre film, technological parameter are prepared by electrostatic spinning technique are as follows: electrostatic spinning voltage is
18kV, solution flow velocity are 0.8mL/h, and receiving distance is 15cm, and temperature is 25 DEG C, relative humidity 40%.It then will be resulting
Polyacrylonitrile micro/nano-fibre film, which is placed at 60 DEG C, to be dried in vacuo, and residual solvent is made sufficiently to volatilize.
S2 carries out plasma modification to polyacrylonitrile micro/nano-fibre film, obtains the bottom plate of a large amount of negative electrical charges of surface band.
Specifically, the polyacrylonitrile micro/nano-fibre film that step S1 is prepared is placed in low-temperature plasma instrument reaction chamber
On interior glass plate, ammonia air valve is opened, its air pressure is made to maintain 0.2MPa or so.Ammonia plasma reaction parameter is set: back
Bottom vacuum degree is 30Pa, gas flow rate 60cm3/ min, power 100W, processing time are 90s.
The zeta current potential and wetability of polyacrylonitrile micro/nano-fibre film after measuring ammonia plasma modification.
The lysozyme of oppositely charged and colloid protein are alternately assembled into bottom plate using layer-by-layer is impregnated by S3
On, until reaching the required double-deck number.
Specifically, water soluble collagen is add to deionized water, is configured to 1mg/mL collagen solution, and adjust
PH to 6.Lysozyme is add to deionized water, is configured to 1mg/mL lysozyme soln, and adjust pH to 6.5.
The modified bottom plate (the hydrophilic polyacrylonitrile micro/nano-fibre film with a large amount of negative electricity) of step S2 is dipped into positively charged
Lysozyme soln in, come into full contact with bottom plate with solution, after twenty minutes take out bottom plate, it is clear using the sodium chloride solution of 0.1M
It washes three times, removes the unassembled successful lysozyme of film surface, form the bottom plate with first layer lysozyme.It again will be with first layer bacteriolyze
The bottom plate of enzyme is dipped into electronegative collagen solution, comes into full contact with film with solution, is taken the film out after twenty minutes, is used
The sodium chloride solution cleaning of 0.1M three times, removes the unassembled successful collagen of film surface, forms band first layer collagen
Bottom plate, so far successfully assemble a bilayer.It is repeated in bottom plate of the above-mentioned formation with first layer lysozyme and forms band first
The step of bottom plate of layer collagen, until the double-deck number reaches 5 or 5.5, drying is to get polyacrylonitrile-lysozyme-collagen
Modified composite micro/nano tunica fibrosa.
In fact, probing by a large amount of test, the present invention creatively passes through plasma modification and impregnates layer by layer from group
Dress makes script micro/nano material that is hydrophobic and should not be used in the fields such as biological medicine, environmental protection have good bio-compatible
Property, promote the performances such as effect, biocidal property, water treatment capacity of cell Proliferation, so as to effectively expand the selection of baseboard material
Range and application range.The present invention does not have any restrictions to the surface charge and wetability of baseboard material, has condition green ring
Guarantor, simple process, it is applied widely the advantages that.
Each technical characteristic of above embodiments can be combined arbitrarily, for simplicity of description, not to above-described embodiment
In each technical characteristic it is all possible combination be all described, as long as however, the combination of these technical characteristics be not present lance
Shield all should be considered as described in this specification.
The foregoing is merely presently preferred embodiments of the present invention, is not intended to limit the invention, it is all in spirit of the invention and
Within principle, any modification, equivalent replacement, improvement and so on be should all be included in the protection scope of the present invention.